JPS6041627A - Purification of mixture comprising water/c1-c2 alcohol/ impurities produced from ethanol industrial manufacture process with extracting agent - Google Patents

Abstract

1. Process for the purification of a mixture of water/C1 -C2 -alcohol resulting from an industrial process for the manufacture of C1 -C2 -alcohol by chemical synthesis characterised in that the mixture to be treated is brought into contact, at least once, with at least one non-toxic gas in the liquid or supercritical state and the extract obtained, containing the impurities, is separated from the purified raffinate.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to the production of C3-C2 alcohols by chemical synthesis or fermentation.
It relates to a method of purification using an alcohol extract. C1~
C2 alcohol is understood to mean methanol and ethanol or a mixture of these two compounds.

BACKGROUND OF THE INVENTION Methanol can be produced, among other things, by direct oxidation of a hydrocarbon bed with molecular methane, by saponification of methyl chloride, or by hydrogenation of carbon oxides. In the course of carrying out these processes, particularly during the surface oxidation process, methanol becomes mixed with formaldehyde, acetaldehyde, acetone, small amounts of acids, higher alcohols and other aldehydes and ketones. Thus, it is necessary to separate methanol from these glaze compounds.

Ethanol obtained by ethanol or by chemical synthesis, especially with ethylene water, contains dissolved organic impurities. body, and which must be removed in order to obtain alcohol with a particularly pleasing flavour.

These impurities include, in particular, diethyl x -te)v, ethers such as ethyl globyl ether and hinatyl ethyl ether, aldehydes such as acetaldehyde, acetone, ketones such as methyl ethyl ketone and diethyl ketone, higher alcohols i.e. C3 -C, alcohol and high molecular compound.

In the case of the synthesis of ethanol by water utilization of ethylene, impurities of the above type are formed in particular in the course of the hydrolysis of ethyl 1JIN acid or the direct hydration of ethylene.

Thus, in the course of the process, a more or less crude alcohol containing these impurities is obtained, which has to be purified.

However, the known purification methods of these C1-C alcohols, namely distillation and solvent extraction methods, are cumbersome and expensive.
It is something that Distillation purification is carried out using dilute C1-C,
This is complicated by the fact that alcohols contain C1-C, both more and less volatile impurities than the alcohol. Also, solvent purification is difficult to observe. This is because complete removal of the solvent from the aqueous phase is always difficult.

The extraction solvent is an extractant, i.e. a JJ-free gas, most commonly in a subcritical state.
te ) in liquid form as well as in supercritical state (5upper
It has been known for a long time to use carbon dioxide in fluid form in critical situations.

Thus, CO2 can be extracted from wine, in particular by flavor (U.S. Pat. No. 3,47S 856, French Patent Application No. 2,505,
No. 616), fat from grains (U.S. Pat. No. 6.939.2)
No. 81) and caffeine from coffee (US Patent #3)
．． 843.832) respectively).

Also, Angewandte Chemie 417
: 10, pp. 701-784 (October 1278)
The international English version of the book contains a very complete σ1 study of gas extraction in supercritical conditions.

Furthermore, French Patent No. 2,466.264 describes a method and a device for extracting ethanol from a water/ethanol mixture with liquid CO7.

However, according to the present invention, most of the impurities dissolved in the water/Ct-C2 alcohol mixture resulting from the industrial process of producing C1-C, alcohols by chemical synthesis or by fermentation are removed from said mixture in excess. Surprisingly and unexpectedly, it is possible to extract in a simple and economical manner a large amount of C8-C, without extracting the alcohol, with a liquid or supercritical gas, preferably COI. was also shown.

SUMMARY OF THE INVENTION Briefly, the present invention seeks to treat in a process for the purification of water/Ct~C, alcohol mixtures resulting from industrial processes for the production of C1~C, alcohols by chemical synthesis or by fermentation. The present invention relates to a process characterized in that the mixture containing the liquid or the at least one non-toxic gas in a liquid or supercritical state is brought into contact at least once with at least one non-toxic gas, and the resulting impure extract is separated from the purified raffinate.

It is preferable to use CO7 as the non-toxic gas, but
This is N, 01SFe, CF3Cl.

CHF, CI, CH2”CFt, Cs Fa, CH
It can be completely or partially replaced by a non-toxic gas selected from among F3, C2Ha, CtH4, etc.

In some processes for producing ethanol, and in most processes for producing methanol, these alcohols are present in a water-free liquid mixture. To apply the method of the invention, a compatible amount of water is added to these mixtures.

In the case of methanol, the water content of the mixture to be prepared is not critical and ranges from 5 to 95% by weight, preferably from 10 to 95% by weight.
It may be 50 weight - 1 inch.

The ethanol content in the water/ethanol mixture may range from about 5% by weight to a content equivalent to a co-water/ethanol mixture (about 95% by weight).

This method is particularly beneficial for C1-C2 alcohols of 10 to 55 degrees.

Thus, although the ethanol content of the treated mixtures resulting from the ethylene hydration process is generally between 20 and 70% and the above impurities of 05 and 20% are present, the process of the present invention does not affect these mixtures. However, it can be applied under 41 profits.

Most of these impurities present in the mixture to be prepared are water/C+~C, C1~C2 alcohols, which are also added to the extractant vessel.
It could never have been expected to have a favorable distribution ratio relative to 1. Second, these impurities are generally C3~
It is less polar than C, alcohols and has a lower conversion rate than C1-C2 alcohols under the temperature and pressure conditions of the contacting process.

This also applies to some of the impurities resulting from the industrial process of producing ethanol by fermentation. Preferably, liquid or supercritical CO2 is used as extraction liquid.

In case of the use of liquid COt, the process is carried out at a temperature of 0 to 31 °C and a pressure of 65 to 600 nm, preferably 10 to
It can be carried out continuously or discontinuously at a temperature of 31 DEG C. and a pressure of about 45 to 1 soz (-L), for example 65/<-L at 20 DEG C.

It is also possible to use supercritical JCO2. In this case yc requires a temperature above 51 DEG C., preferably above 35 DEG C., and a pressure between 73 and 550 bar, preferably between 100 and 270 bar.

The method according to the invention can be operated continuously or discontinuously.

In continuous operation, the liquid or supercritical C02 feed weight 'A
The ratio of 1' to the feed concentration of the mixture to be treated is from 1 to joO, preferably from 2 to 10.

In discontinuous operation, from 1 to 100 Kg per Kg of mixture I
of CO2 is preferably used, preferably 2 to 10 to 9 of CO2.

The maximum amount of CO that should be used essentially depends on the impurity content, the concentration of C8-C, alcohol in the mixture to be treated, and how much C8-C, alcohol is carried away by the CO, an acceptable loss. This is a function that determines the level.

The CO2 becomes loaded with an ethanol-rich extract that is highly enriched in impurities, and on the other hand the residual mixture (referred to as raffinate)
Although it is slightly deficient in 01-c2 alcohol, it practically no longer contains any impurities.

Contacting the mixture to be treated with a liquid or supercritical CO is carried out continuously or discontinuously under pressure in a conventional liquid extraction apparatus (6).

In a discontinuous process, the mixture to be purified is contacted with liquid or supercritical CO2, preferably in a pressure-resistant reactor equipped with stirring means, for example in an autoclave equipped with a stirrer. CO2 becomes loaded with impurities along with small amounts of C8-C and alcohol. Also,
It is possible and even absent to implement this method continuously. In this case, the liquid or supercritical CO7 and the mixture to be treated are continuously introduced into a pressure-tight reactor optionally equipped with heating and stirring means.

To obtain good separation of liquids, pulsating columns, packed columns,
It is particularly possible to use mixing/sedimentation equipment, t-ray type columns, baffles, ratchet-type devices, microporous filters or glass materials, provided that the equipment used can withstand the working pressure. shall be taken as a thing.

Alternatively, the mixture to be treated can be converted into CO2 by a nozzle or other system.
It is also possible to hide it inside. It is advantageous to carry out the extraction in a circular flow manner. In this case, an extraction column is used as the reactor. The mixture to be purified is injected at the top of the extraction column, the bottom of the column is fed with liquid or supercritical CO2, and the purified mixture is continuously withdrawn at the bottom of the column, containing impurities and a small amount of C5-C2 alcohol. The CO7 is withdrawn at the top of the column, this phase is fractionated in a pressure device, the impurities are recovered in the form of water/C1-C2 alcohol extract, and the CO2 is recycled to the extraction column after returning to the extraction conditions. Beneficial. The impurities concentrated in the extract (mixture of ethanol-enriched water and 01-C2 alcohols) can have very different properties. For example, in the case of ethanol, these may be more volatile than ethanol (e.g. diethyl ether and acetaldehyde), or the same volatility as ethanol (methyl ethyl ketone), or less volatile than ethanol (diethyl ketone). , n-butanol, butan-2-ol, etc.). However, in general, the best results are obtained when the impurities in question are higher alcohols, ethers, ketones, aldehydes, esters or mixtures of these types of compounds and generally non-polar compounds.

By using this method, an impurity concentration ratio of 6 to 10'8 degrees can be obtained, and in some cases this ratio can be greater than 10. This impurity concentration ratio (K) is determined by the following formula %: 2 (where ■ represents the weight ratio of impurities/ethanol in the extract containing CO6, and K represents the weight ratio of impurities/ethanol in the extract containing CO6, and
water in equilibrium with phase 1/impurities in the C1-C2 alcohol phase/representing the weight ratio of C+-C2 alcohol).

Separation of liquid or supercritical CO2 and impurities loaded with CO2 can be carried out by various physical means such as increasing the temperature during the extraction step, reducing the pressure or using absorbents. In the case of liquid COt, simple distillation can be used.

Concentrated impurities in the form of a degassed water/C+ to C2 alcohol extract enriched with impurities can be separated, for example by dilution of this extract with water, according to an advantageous embodiment of the method of the invention. It can be divided by manipulation followed by settling. C1~C
The aqueous phase containing the di-alcohol is recycled to the extraction stage and the organic phase containing impurities is removed. By performing this separation operation, virtually all loss of C1-C2 alcohols is avoided.

The impurity-enriched extract contained in the liquid or supercritical CO7 can be recovered by simple distillation of the CO7 at pressures below the critical pressure. Thus, if supercritical CO2 is used, a pressure drop is required (pressure above critical pressure, temperature above critical temperature). This distillation often requires only a few theory plates. This is because COI is much more volatile than water, C1-C, alcohol or any of the impurities.

Distillation requires little energy if operated near the critical point. For example, the heat of vaporization of liquid CO2 is only 29 Kca per C0, IKf at 65 bar and 23°C.
It is l. This distillation is carried out at low temperatures (15 to
temperature (25°C) and thus a low heat level heat source (
This makes it possible to use i-1: (inexpensive). The gaseous Co2 recovered at the top of the distillation column can be condensed and then recycled to the column.

According to an even more preferred embodiment of the invention, water/C+
= A mixture of CtC2 alcohols/products is brought into contact with liquid CO1 at least once, on the one hand, liquid CO containing most of the impurities and a small amount of 01-C2 alcohol
2 phases, and on the other hand a purified raffinate containing substantially all of the C3-C2 alcohol used and a small amount of CO7, the liquid CO1 phase is separated from the purified raffinate, the raffinate thus produced is recovered, and A degassing operation is carried out to allow the removal of CO7, and the liquid CO2 phase is distilled to produce a gaseous phase of purified CO2 and a liquid phase essentially made up of impurities and a small amount of C8-C2 alcohol. The gaseous CO1 phase is condensed and recycled to the initial contacting step and, if desired, impurities and small amounts of C,- The impurities are recovered by subjecting the liquid phase consisting of C, alcohol to the separation operation described above, and the aqueous phase containing C8 to C, alcohol is recycled to the contacting step.

The preferred method described above can be carried out industrially in the apparatus shown schematically in FIG. 1 of the accompanying drawings.

To illustrate this figure, the apparatus 10'i consists essentially of the tray column 3. A mixture of water/C+ to C and alcohol to be purified is supplied to the top via a pipe 5, and liquid CO2 is supplied to the bottom.

Purification takes place and the purified water/C3-C, alcohol mixture is continuously withdrawn at the bottom of the column via a line 7 equipped with a valve 9. This piping includes an outlet 13 for Co2 and an outlet 15 for purified mixture of water/C5-C2 alcohol.
It is connected to a degassing tower 11 equipped with. Liquid CO2 loaded with impurities is continuously withdrawn in m parts of the column,
Then, it flows into a pressure-resistant autoclave 19 via a pipe 17, where distillation is carried out.

The extract containing impurities dissolved in a small amount of C,-C2 alcohol is transferred to the If? 21 at the bottom of the autoclave and enters a degassing column 25 with an outlet 27 for gaseous CO2. The extract is introduced into a container 61 equipped with an agitator 33 and a water inlet 35 via a pipe 29 and subjected to a separation operation.

The resulting mixture is sent to settling tank 69 via piping 37.

The organic layer containing impurities is extracted through the pipe 41,
And the aqueous layer containing C7-C2 alcohol is pipe 4
5 and recycled to the top of the column. Gaseous CO7 is withdrawn from the autoclave 19 via line 47, enters the condenser 49, and is recycled to the bottom of the column via line 55 by the atomizer 51 after being topped with CO7 via line 56. .

The method according to the invention has a number of benefits. For example, very good transfer rates between the COt phase and the phase of the mixture to be purified are achieved, which reduces the bulk of the equipment, and COl is much more volatile than the impurities dissolved in it. Because of the high CO6, it is possible to enjoy extremely easy separation of CO6 and impurities. Moreover, in the illegal practice, the separation of COI and impurities requires little energy expenditure. Furthermore, the partition coefficient K is high and CO, compared to the non-toxic gas used, is C1
~C, does not leave any trace in the alcohol.

Other benefits and features of the invention will become apparent from the following examples, which are intended to be merely illustrative of the invention and are not intended to limit it in any way. Okay then.

Example 1 Discontinuous operation on a water/ethanol/impurity mixture In this example, the apparatus shown schematically in FIG. 2 is used. In this figure, the device 101 includes a source 103 of CO at 50 bar and a vessel 11 with an outlet 113.
1 and a compressor 105 supplying CO2 to an autoclave 107 with a pressure relief valve 109 connected to the autoclave 107. The water/ethanol/impurity mixture 115 to be purified is charged to an autoclave 107, and the autoclave is placed under CO2 pressure from a source 103 (
sobar, 15°C). The pressure is increased to approximately 95 bar by compressor 105 and the temperature in the autoclave is approximately 26°C.

At this point, the pressure release valve 109 on the downstream side of the autoclave 107 is opened while the pressure in the autoclave 107 is maintained constant by the compressor 105. The liquid CO2 dispersed by the glass-metal plate 117 passes through the mixture 115 charged to the autoclave and becomes loaded with extract, then the pressure relief valve 109
from 95 bar to 1 bar. Extract 119 is collected in container 111. Predetermined weight C
When the 02 is cycled, the autoclave is returned to atmospheric pressure. A sample of the residue or raffinate contained within the autoclave is taken.

The entire operation is restarted as many times as necessary to fractionate the extract, and in this manner a series of extracts and residues is obtained. These are analyzed by gas chromatography.

In an autoclave, add a water/ethanol mixture of 48I (M) to ah (this composition is shown in Table 1).
Charge. In the charged mixture, liquid Co, (95
bar, 22°C) into three consecutive portions (155 g, 155
g and 2oog). Each part 1 (i=1.2
．． 3) dissolves extract Ei and obtains raffinate Ri. Extract Ei is recovered by releasing the CO7 pressure. The continuous extract Ei and the continuous raffinate R1 are analyzed by chromatography.

The results are summarized in Table 1 below. These are expressed in ppm in the case of impurities and in % weight in the case of ethanol.

The distribution ratio K of various impurities is shown in Table 2 below.

The following abbreviations are used in each table:

MEC Ac0Et representing methyl ethyl ketone 1-PrOH representing ethyl acetate EtOH representing isopropanol DEC representing ethanol M2B2 representing diethyl ketone g- representing 2-methylbutan-2-ol
BuOH n-PrOH representing sec-butanol 1-BuOH representing n-propanol P3 representing isobutanol P2 representing pentan-3-ol n-BuOH representing pentan-2-ol INI representing n-butanol Table representing unidentified impurities From Table 1 and Table 2, it can be seen that the concentration factors for all impurities remain around 10 during the purification run.

Example 2 Continuous treatment of a water/ethanol/impurity mixture In this example, the apparatus shown schematically in FIG. 3 is used. As can be seen from this figure, the device 361 includes a perforated tray 665
It consists of a tower 663 having a

It has 16 stages and a height of 75 feet per stage. The liquid CO2 forms the dispersed phase and the mixture to be made forms the continuous phase. The mixture to be purified is pumped between O and O by a diaphragm pump 668.
A flow rate of 700 Cm''/h is introduced at the top of the column via line 667 and withdrawn at the bottom of the column via line 669.

Liquid or supercritical CO2 is fed at the bottom of the column via line 341 (0-2 Q, 000 cm3/h) and withdrawn at the top via line 646. Tower Co1
The pressure is regulated by a regulating system 347 and the level of the mixture is regulated 111 by a level regulator. Withdrawal of the purified mixture at the bottom of the column is carried out by a 2 cm" long chamberer 645 regulated by a Leher system. Piping 346 carries the extract to a regulating system 547, a riser 649 and then to a 41 sub-chamber 651. There, the evaporation of CO2 and recovery of extract are photonized.The distilled CO7 is transferred to pipe 3.
56 is sent to the compressor 355, but this transfer
Adjusted to CO□ of Nin'/h.

The liquid CO2 is supplied to the liquid CO2 via a cooling device 1361 (which has a 20"
C), and then send the liquid C02 ("distribution a341
sent to.

All piping consists of 2.41 diameter stainless steel tubing. The highest pressure f, li that this device 6' can withstand is 250 bar.

The following 10 tests were conducted at ambient temperature.

Experiments C22 and C25 are carried out with a water/ethanol/impurity mixture feed containing about 27% ethanol.

Tests C24, C25, C26 and C27i-4, Test C
Tests C28, C29, C601ft, and C31 are performed with a 24-fold dilution of the mixture feed of tests C22 and C23.

Table 3 below shows the operating conditions for each test: extraction column pressure, distillation autoclave pressure, liquid CO.

flow rate, supply amount of the mixture to be purified, withdrawal amount of the purified mixture, withdrawal from the distillation autoclave 171,
and stipulates ethanol venus of feed, drawn matter and extracts. The last column of Table 6 also defines the proportion of the dispersed phase (liquid CO,) retained in the column.

The duration of each test is at least 2 hours, and the contents of the column are replaced at least 6 times with niJ, which is considered stable for operation of the apparatus. As shown in Table 6, the ethanol content values of the material withdrawn from the column are found to be close to each other, thus indicating that the operation of the unit is very stable. In high COt flowmeters, 660 cm3 of the mixture to be purified is placed at the top of the O column where column overflow problems occur.
/h and at the bottom of the column the material is
It is extracted at a rate of cm3/h. At the bottom of the distillation autoclave, the theoretical socm
Instead of h, only about 65-45 c+n'/h are recovered.

When certain operating conditions are reached, impurities ( with a confirmed chemical formula).

Results 2 are summarized in Table 4 below. The peak factor is 1. The numbers in each column of Table 4 will be explained below.

Tests C22 and C25 tested the flow rate of the mixture to be purified at 630 CI! ”/h and two liquid CO2
The flow rates of 5 and 6 and 2 kg/h are carried out, respectively. Comparing C6 and Paulownia 4, it can be seen that the purification operation is efficient at [σ] where most of the impurities are completely or almost completely removed. Comparing column 5 with column 4, C
It has been shown that the purification efficiency decreases when the flow rate of O, is decreased from 5.6 kg/h to 2 kP/h. Numbers 6 and 2 indicate the content of impurities in the material withdrawn from the autoclave.

These components are extremely high and the concentration factor obtained between 6 and 6 is greater than 10.

Tests C24-C25-C26-C27 This procedure is the same as that of tests C22 and C26,
And the results are shown in Table 4. 8 and 9 are f1
1 represents the analysis of the column feed of the mixture to be prepared.

However, tests C24-C25 have a flow h1 of the mixture to be purified of 620 cm5/h and two liquid CO! the flow rates of 4.5 and 6 kl/, respectively.
It was carried out as h. In contrast, test C2
6 and C27 are stream ii 2 of the mixture to be purified.
50 cm'/h and the flow rates of the two liquid COs were 46 and Z4 #/h, respectively.

From Table 4, it can be seen that the higher the ratio of the flow rate of CO1/air flow of the mixture to be purified, the more efficient it is.

If we compare runs C221i and c24 (4147 and 10), for liquid CO and comparable bIE properties of the mixture to be purified, the purification efficiencies are similar and the ethanol losses are comparable (in run C22 the ethanol content is 2
4.65J<14% to 2a bookscape% and test C24
124 weight 1% to 10.2 points m%). This is G
′! , this continuous process of yuzu seems to indicate that the extractability of impurities cannot be changed by changing the dilution of the mixture to be purified.

Tests C2B-C29-C50 This process is carried out under the same conditions as for Tests C24-C27 above. The results are presented in Table 4 below.

[Brief explanation of the drawing]

FIG. 1 is a schematic flow diagram of implementing one method according to the present invention. FIG. 2 is a schematic flowchart for discontinuously carrying out the method according to the invention. FIG. 3 is a schematic flowchart for continuously carrying out the method according to the invention.

Claims (1)

Scope of Claims: (1) A mixture of C1 to C2 a produced by chemical synthesis or fermentation is brought into contact at least once with a non-toxic gas of at least one glaze in a liquid or supercritical state, and the resulting impurity-containing A method for purifying a water/C, -C, alcohol mixture, characterized in that the extract is separated from the purified raffinate. (2) Water to be purified/C+~C2 alcohol/
2. Process according to claim 1, characterized in that the mixture of impurities results from a C1-C2 alcohol/impurity mixture with appropriate addition of water. (3) The method according to claim 1 or 2, which is carried out continuously or discontinuously. (4) The method according to any one of claims 1 to 3, wherein the gas used is CO2. (5) 4. Liquid CO2 at a temperature of 0-31°C and a pressure of 35-600 bar is used. The method according to claim 4, wherein the method has J characteristics. (6) The temperature is 20~30℃ and the pressure is 45~
5. A method according to claim 4, characterized in that the pressure is 150 bar. 5. Process according to claim 4, characterized in that f7) super-superior CO7 at a temperature of more than 35[deg.] C. and a pressure of 77) to 650 bar is used. (8) being carried out continuously and using a ratio of 1 to 100, preferably 2 to 10, of the weight flow of liquid or supercritical CO2 to the weight flow rate of the mixture to be treated; A method according to any one of claims 4 to 7. (9) Claims characterized in that it is carried out discontinuously and that from 1 to 100, preferably from 2 to IOK, of foam or criticality ≦ filtration C02 is used per 1 mixture. The method according to any one of items 4 to 7. 00) Contact process force; extraction J? The extraction at step 1 is carried out by extraction, the purified mixture is injected into the m part of the extraction column, and the liquid or supercooker COt is fed to the bottom of the column;
The produced mixture is continuously withdrawn at the bottom of the column and the CO2 containing undesirables and small amounts of 01-C2 alcohols is removed.
is discharged at the top of the column, this same phase is fractionated in a pressure device 1 lar, the impurities are recovered in the form of degassed water/C+~C2 alcohol extract, and the Co2 is returned to the extraction conditions. 1 to be recycled to the extraction column
1! 9. The method according to claim 8. (11) The extract is further fractionated to separate 002 from impurities in the alcohol solution, and after the CO2 is returned to the extraction conditions of the extraction step, it is circulated through a ladle. The method according to any of Item 9. (12) The method according to claim 2B11, wherein when liquid C02 is used, the separation is simple distillation. (13) 719 mixtures of water/C1-Ct alcohol/impurities are brought into contact with liquid COt at least once, while a liquid CO2 phase containing most of the impurities and a small amount of C0-C2 alcohol; On the other hand, a purified rough oxide containing all of the C1-C2 alcohol used and a small amount of CO7 is formed, and the liquid CO7 phase is separated from the purified raffinate, and the raffinate thus produced is and collect it with liquid CO
BSA gas 5, which allows the removal of 2, is applied, and the liquid COz phase is distilled to form purified CO1 gas (4, as well as impurities and small amounts of C1-C, alcohols). producing a liquid phase (this liquid phase is degassed and referred to as water/C+~C. alcohol extract), and the gaseous CO is condensed into the phase and recycled to the initial bonding process. 12. The method according to claim 11, characterized in that O4) degassed water obtained after removal of CO2/C0
-C2 alcohol extract is subjected to a separation operation by dilution with water, the mixture is allowed to settle, the organic phase is removed, and the aqueous phase containing the C5-C2 alcohol is recycled to the extraction process. The method according to any one of claims 10 to 13. 09 The water/C+~C2C0~C2 alcohol/compound to be made into a sheath is produced from the process of synthesizing ethanol by water utilization of ethylene.
The method according to any one of claims 1 to 14η1.